In situ synchrotron powder X-ray diffraction (PXRD) study was conducted on sodium and potassium tetrafluoroborate (NaBF 4 and KBF 4 ) to elucidate structural changes across solid−solid phase transitions over multiple heating−cooling cycles. The phase transition temperatures from diffraction measurements are consistent with the differential scanning calorimetry data (∼240 °C for NaBF 4 and ∼290 °C for KBF 4 ). The crystal structure of the high-temperature (HT) NaBF 4 phase was determined from synchrotron PXRD data. The HT disordered phase of NaBF 4 crystallizes in the hexagonal, space group P6 3 /mmc (no. 194) with a = 4.98936(2) Å, c = 7.73464(4) Å, V = 166.748(2) Å 3 , and Z = 2 at 250 °C. Density functional theory molecular dynamics (MD) calculations imply that the P6 3 / mmc is indeed a stable structure for rotational NaBF 4 . MD simulations reproduce the experimental phase sequence upon heating and indicate that F atoms are markedly more mobile than K and B atoms in the disordered state. Thermal expansion coefficients for both phases were determined from high-precision lattice parameters at elevated temperatures, as obtained from Rietveld refinement of the PXRD data. Interestingly, for the HT-phase of NaBF 4 , the structure (upon heating) contracts slightly in the a−b plane but expands in the c direction such that overall thermal expansion is positive. Thermal conductivities at room temperature were measured, and the values are 0.8−1.0 W m −1 K −1 for NaBF 4 and 0.55−0.65 W m −1 K −1 for KBF 4 . The thermal conductivity and diffusivity showed a gradual decrease up to the transition temperature and then rose slightly. Both materials show good thermal and structural stabilities over multiple heating/cooling cycles.